X -diamino-stilbene compounds



United States Patent 4,4'-DIAl\/IlN0-STILBENE COMPOUNDS Heinrich Gold, Opladen, and Siegfried Petersen, Leverkusen, Germany, assignors to Farhenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Application November 3, 1953, Serial No. 390,081

Claims priority, application Germany August 28, 1950 7 Claims. (Cl. 260-249.6)

The present invention relates to new 4,4-diamino stilbene compounds and to a process of producing them.

This application is a continuation-in-part of our application Serial No. 241,692, filed August 13, 1951, entitled 4,4-Diamino-Stilbene Compounds.

The 4,4'-diaminostilbene compounds of the present invention may be obtained by reacting one mol of 4,4- diamino-stilbene or its derivativescontaining sulfonic acid or carboxylic acid groups with two mols of cyanuric chloride and one mol of an aromatic amine, which carries at least two aromatic nuclei linked by a carbonamide group and preferably contains solubilizing groups.

Typical representatives of the new compounds correspond, for instance, to the general formula:

N HY

YHN

group, a sulfonate or a carboxylate group, one Y indicates hydrogen or a substituent, such as an alkyl, aryl or acyl radical and the other Y represents the monovalent radical of the reaction product of 1 mol of a 4,4'-diamino-stilbene-disulfonic acid in the form of a water soluble salt and 2 mols of cyanuric chloride, said monovalent radical corresponding to the general formula:

Z Z and Z standing for equal or different substituents, for instance, chlorine, hydroxy groups and/ or amino groups which may contain alkyl-, hydroxyalkylor aryl radicals.

The new compounds of the invention may be obtained in various manners, for instance, by reacting the condensation product obtained from 1 mol of 4,4-diaminostilbene-disulfonic acid and 2 mols of cyanuric chloride with 1. mol of p-amino-benzoyl-p-phenylene-diamino-sulfonic acid, 1 mol p-amino-benzoyl-ethyl-p-phenylene-diamino-sulfonic acid, 1 mol p-amino benzoyl-phenyl-pphenylenediamino-sulfonic acid or 1 mol p-amino-benzoylacetd-p-phenylene-diamino-sulfonic acid respectively. If the chlorine at the triazine nuclei is to be replaced by the hydroxyl group, the reaction product is boiled in aqueous alkali, for instance, sodium carbonate. By reacting the product with ammonia or primary or secondary amines,

SOaH

the chlorine at the triazine nuclei is likewise easily replaced by the corresponding amino radicals. If the above mentioned condensation product is caused to react with 1 mol of p-amino-benzoyl-p-phenylene-diamino-sulfonic acid, an organic acid radical may be introduced into the ice free amino group by treating it with an acylating agent whereby chlorine present in the triazine nuclei may be removed by means of ammonia, amines or sodium carbonate, either before or after the treatment of the free amino group with an acylating agent.

The compounds of the present invention may be employed, for instance,as optical bleaching agents by treating the goods to be bleached in aqueous solutions containing the new compounds. The novel compounds may also be incorporated in detergents or may be added to the washing liquors.

The novel compounds may advantageously be used for increasing the white efiiects of undyed materials of any kind, especially textiles, ordinary and special paper, for instance photographic paper, straw for hats, leather, woods, soaps, etc.; also dyed materials are improved by the novel compounds which in many cases effect a clearer and brighter shade. For producing improved discharges on dyed textiles the compounds of the invention may either be incorporated in the dyestuff or may be added to the dyeing liquor or finally to the discharge paste.

The novel compounds of the present invention display when used as bleaching agents the advantage over the previously known optical bleaching agents that the bleach ing effects obtained therewith are extraordinarily fast to washing and in many cases even stable to boiling.

The invention is further illustrated by the following examples without being restricted thereto, the parts given being by weight:

Example 1 54 parts of cyanuric chloride are dissolved in 350 parts of warm acetone and the resulting clear solution is poured into a mixture consisting of 400 parts of ice and 300 parts of Water. 95 parts of the sodium salt of 4,4-diamino stilbene-2,2'-disulfonic' acid dissolved in 400 parts of water and 15 parts of sodium carbonate dissolved in 100 parts of water are simultaneously added with stirring so that the reaction mixture is always acid to Congo. The temperature is kept at 0 C. After the 4,4-diarnino-stilbene- 2,2'disulfonic acid has been completely reacted 14 parts of aniline are added, the reaction mixture is slowly heated to 25 30" C. while keeping the reaction mixture Weakly acid to neutral by dropping in parts of 10% caustic soda solution. To this suspension of the sodium salt of 4-[2-chloro-4-phenylamino-1,3,5 triazyl-( 6)l-4'-[2,4-dichloro-1,3,5-triazyl-(6)l-diamino-stilbene 2,2 disulfonic acid, 48 parts of the sodium salt of 2-(4'-arninobenzoyl-amino) 5-amino benzene-sulfonic acid dissolved in 200 parts of water are added, the reaction mixture is heated to 60 C. and kept neutral to weakly acid by adding 75 parts of 10% sodium carbonate solution. Thereupon 250 parts of 20% ammonia are added, the acetone is distilled oif and the reaction mixture is heated to C. for a further two hours. 600 parts of sodium chloride are added at 95100 C. and the precipitate formed is separated by filtering at 50 C after drying parts of a weakly yellow powder are obtained.

Example 2 54 parts of cyanuric chloride are condensed with 95 parts of the sodium salt of 4,4'-diamino-stilbene-2,2-disulfonic acid as described in Example 1, whereupon the condensation product is reacted with 14 parts of aniline. To the sodium salt of 4-[2-chloro-4-phenylamino-1,3,5- triazyl (6)] 4 [2,4 dichloro 1,3,5 triazyl (6)]- diamino-stilbene-Z,2'-disulfonic acid obtained, 50 parts of the sodium salt of 2-(4-amino-benzoyl-amino)-5- acetyl-amino-benzene-sulfonic acid dissolved in 200 parts of water are added, the reaction mixture is heated to 60 C. and kept neutral to Weakly acid by adding 75 parts of 10% aqueous sodium carbonate solution. The precipitate formed is separated by filtering. After drying 160 parts of a weakly yellow powder are obtained.

Exampie 3 150 parts of the end product obtained according to Example 2 are suspended in 2000 parts of water and reacted with 30 parts of monoethanolamine at 95l00 C. for two hours. 600 parts of sodium chloride are added at 95100 C. and the precipitate formed is separated by filtering at 50 C. After drying 164 parts of a weakly yellow powder are obtained.

When replacing in the above reaction 30 parts of monoethanolamine by 250 parts of a 33% aqueous solution of monomethylamine of by 230 parts of a 39.5% aqueous solution of a monoethylamine, 163 parts or 152 parts respectively of a pale yellow powder are obtained.

Example 4 54 parts of cyanuric chloride are condensed in aqueous acetone with 95 parts of the sodium salt of 4,4'-diaminostilbene-2,2-disulfonic acid as described in Example 1, whereupon the condensation product is reacted with 16 parts of p-toluidine. To the sodium salt of 4-[2-chloro- 4 p tolylamino 1,3,5 triazyl (6)] 4 [2,4 dichloro 1,3,5 triazyl (6)] diamino stilbene 2,2- disulfonic acid obtained 52 parts of the sodium salt of 2 (4 amino benzoyl amino) ethylaminobenzene-sulfonic acid dissolved in 200 parts of water are added, the reaction mixture is heated to 60 C. and kept neutral to weakly acid by adding 75 parts of 10% aqueous sodium carbonate solution. Thereupon 400 parts of 10% aqueous solution of sodium carbonate are added, the acetone is distilled off and the reaction mixture is heated to 95-100 C. for a further two hours. 600 parts. of sodium chloride are added at 95100 C. and the precipitate formed is separated by filtering at 50 C. After drying 160 parts-of a weakly grey powder are obtained;

Example 5 To the aqueous acetone suspension of the sodium salt of 4 [2 chloro 4 phenylamino 1,3,5 triazyl- (6)] 4' [2,4 dichloro 1,3,5 triazyl (6)]- diarnino-stilbene-2,2-clisulfonic acid obtained from 54 parts of cyanuric chloride, 95 parts of the sodium salt of 4,4-diamino-stilbene-2,2'-disulfonic acid and 14 parts of aniline according to Example 1, 59 parts of the sodium salt of 2-(4-amino-benzoyl-amino)-5-phenyl-amino-benzene-sulfonic acid dissolved in 200 parts of water are added, the reaction mixture is heated to 60 C. and kept neutral to weakly acid by adding 75 parts of 10% aqueous sodium carbonate solution. Thereupon 30 parts of monoethanolamine are added, the acetone is distilled off and the reaction mixture is heated to 95-100 C. for a further two hours. 600 parts of sodium chloride are added at 95100 C. and the precipitate formed is separated by filtering at 50 C. After drying 156 parts of a greyish-yellow powder are obtained.

When replacing in the above reaction 30 parts of ethanolamine by 250 parts of a 33% aqueous solution of monomethylamine or by 230 parts of a 39.5% aqueous solution of monoethylamine, 180 parts or 200 parts respectively of a likewise greyish-yellow powder are obtained.

The new compounds are employed as optical bleaching agents in the following manner:

Cotton is treated at 40 C. for 15 minutes in a liquor of 1:20 containing per liter 0.04 gram of any of the above powders. The goods are subsequently rinsed and dried. The white effects of the goods thus treated are essentially improved and retained even after usual laundering several times.

If in the usual manufacture of paper 0.1-1 part of any of the above powders is added to parts of sulfite cellulose in the beater, the paper obtained shows a pleasant, neutral white tint.

lf yellowish White paper is treated in a solution containing per liter 0.05-0.06 gram of any of the abo e powders the paper shows a neutral white after rinsing and drying.

Laundering is carried out as usual by means of a detergent containing per 1 kilogram besides the usual additions 23 grams of any of the above powders. After rinsing and drying the laundry goods have a pure, white appearance.

We claim:

1. 4,4-diamino-stilbene compounds of the general formula wherein Z1, Z2 and Z3 stand each for a member of the group consisting of chlorine, the hydroxy group, the amino group, an amino group substituted by a lower alkyl radical, an amino group substituted by a lower oxalltyl radical, and an amino group substituted by aryl radical, whereas Y represents a member of the group consisting of hydrogen, an alkyl radical, an aryl radical and an OC-hydrocarbon radical.

2. A 4,4-diamino-stilbene compound of the general formula of claim 1 wherein Z1 stands for the amino group, Z2 for the phenylamino group and Z3 for the amino group, whereas Y represents hydrogen.

3. A 4,4'-diamino-stilbene compound of the general formula of claim 1 wherein Z1 stands for the monoethanolamino group, Zz for the phenylamino group and Z3 for the monoethanolamino group, whereas Y represents the acetyl group.

4. A 4,4'-diamino-stilbene compound of the general formula of claim 1 wherein Z1 stands for the mono ethylamino group, Z2 for the phenylamino group and Z3 for the monoethylamino group, whereas Y represents the acetyl group.

5. A process of producing 4,4-diamino-stilbene compounds which comprises reacting one moi of a 4,4-diamino-stilbene-disulfonic acid with two mols of cyanuric chloride and one mol of an aromatic diamine of the general formula NHY wherein Y represents a member of the group consisting of hydrogen, an alkyl radical, an aryl radical and an OC-hydrocarbon radical.

6. A 4,4'-diamino-stilbene compound of the general formula of claim 1 wherein Z1 stands for the hydroxy group, Z2 for the tolylamino group and Z3 for the hydroxy group, whereas Y represents the ethyl group.

7. A 4,4-diamino-stilbene compound of the general formula of claim 1 wherein Z1 stands for the monoethanolarnino group, Z2 for the phenylamino group and Z3 for the monoethanolamino group, Whereas Y represents the phenyl group.

No references cited. 

1. 4,4''-DIAMINO-STILBENE COMPOUNDS OF THE GENERAL FOR MULA 